Spiral chiral perpyraene derivative, preparation method thereof and organic electronic device

Abstract

The invention provides a spiral chiral perpyraene derivative, a preparation method thereof and an organic electronic device, and relates to the technical field of organic functional materials. The spiral chiral perpyrarene derivative has a multiple spiral chiral structure, is doped with boron-oxygen double heteroatoms, and has excellent stability, moderate light-emitting quantum efficiency, multi-site Lewis acidity, light-emitting wavelength dynamic regulation and control performance, circular polarization light-emitting performance and reversible oxidation-reduction performance. According to the preparation method, 2, 2 ', 6, 6'-tetrabromo-1, 1 ': 4', 1 '-terphenyl and 2, 12-di-tert-butyl-7-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl)-5, 9-dioxo-13B-'and [3, 2, 1-DE] anthracene are taken as precursors and are subjected to palladium catalytic coupling and intramolecular oxidative dehydrocyclization reaction initiated by ferric trichloride to synthesize the compound, and the preparation method is simple to operate and excellent in yield.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic functional materials, and particularly relates to a helical chiral peropyrene derivative, a preparation method thereof and an organic electronic device. BACKGROUND

[0002] As a fragment structure of graphene, polycyclic aromatic hydrocarbons have become one of the core functional materials in the field of organic optoelectronics due to their tunable conjugated system, excellent photophysical properties and electron transport performance, and have shown wide application prospects in flexible electronics, display devices and other frontier applications. Among them, peropyrene, as a typical polycyclic aromatic hydrocarbon structural unit, is composed of perylene units extended by edge benzene rings, and has the following characteristics: in common organic solvents, its ultraviolet-visible absorption wavelength is concentrated in the range of 400-500 nm, the luminescence quantum efficiency is as high as 0.94, and it shows good photophysical properties, and is an ideal precursor for constructing efficient organic chromophores; in addition, the rigid planar structure of peropyrene molecules enables intermolecular π-π stacking to form ordered aggregates, thereby significantly improving the carrier mobility and exhibiting important potential in organic semiconductor materials.

[0003] In order to further expand the functional boundaries of peropyrene materials, researchers have tried to introduce multiple helical chiral structures into the skeleton of peropyrene, which can endow peropyrene materials with unique chiral optical properties such as circular dichroism absorption (CD) and circularly polarized luminescence (CPL) characteristics. Such properties are key requirements in the fields of chiral OLEDs, chiral sensing, asymmetric catalysis, etc., making helical chiral peropyrene derivatives a research hotspot in the field of chiral functional materials.

[0004] In the performance regulation strategy of helical chiral peropyrene, introducing heteroatoms such as nitrogen, oxygen and sulfur into its skeleton is one of the most effective means to regulate its electronic structure and luminescent properties: the electronegativity and atomic radius difference of heteroatoms can change the molecular frontier molecular orbital energy level and conjugated system electron cloud distribution, thereby realizing precise regulation of core parameters such as absorption / emission wavelength, luminescence quantum efficiency, redox potential, etc.

[0005] However, the chiral designs of existing peropyrene derivatives are mostly concentrated in single-helix or non-conjugated helix structures, resulting in limited chiral structure and poor chiral stability. Furthermore, existing peropyrene derivatives containing heteroatoms either focus solely on optimizing luminescence performance (such as improving quantum efficiency) or solely on modulating electron transport performance, failing to achieve simultaneous multifunctional synergy. These limitations restrict the depth and breadth of peropyrene derivative applications in organic electronics, sensing, and chiral optics. Therefore, overcoming these shortcomings of existing peropyrene derivatives has become crucial for promoting their application in organic electronics, sensing, and chiral optics. Summary of the Invention

[0006] To address the shortcomings of existing technologies, this invention provides a helical chiral peropyrene derivative, its preparation method, and an organic electronic device. The helical chiral peropyrene derivative exhibits excellent stability, moderate luminescence quantum efficiency, multi-site Lewis acidity, dynamic modulation of emission wavelength, circularly polarized luminescence performance, and reversible redox properties.

[0007] The specific technical solution of this invention is as follows: In a first aspect, the present invention provides a helical chiral peropyrene derivative having a structure as shown in Formula I:

[0008] In one possible implementation, the helical chiral peropyrene derivative is: using 2,2”,6,6”-tetrabromo-1,1':4',1”-terphenyl and 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene as precursors, a peropyrene derivative with extended boron-oxa double[7] helical chirality is synthesized by palladium-catalyzed coupling and intramolecular oxidative dehydrogenation cyclization reaction initiated by ferric chloride.

[0009] Secondly, the present invention provides a method for preparing the above-mentioned helical chiral peropyrene derivative, comprising the following steps: S1, 1,3-dibromo-2-iodobenzene and 1,4-phenylenediboronic acid were coupled via a palladium-catalyzed Suzuki reaction to give 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl; S2, dibromo-1,4-difluorobenzene and 4-tert-butylphenol undergo an aromatic nucleophilic substitution reaction in the presence of potassium carbonate to give 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene); S3, the 4, 4'-((2, 5-dibromo-1, 3-phenylene) bis (oxygen)) bis (tert-butylbenzene) described in step S2 is subjected to lithiation reaction with n-butyllithium to generate lithium reagent, and then subjected to step-by-step reaction with boron tribromide, that is, first, the directional introduction of boron atom at a specific position of the aromatic ring is realized through aromatic electrophilic substitution reaction, and then the six-membered boron oxygen heterocyclic structure is constructed through direct carbon-hydrogen bond boronation reaction, to obtain 7-bromo-2, 12-di-tert-butyl-5, 9-dioxo-13B-bora-naphthacene [3, 2, 1-DE] anthracene; S4, the 7-bromo-2, 12-di-tert-butyl-5, 9-dioxo-13B-bora-naphthacene [3, 2, 1-DE] anthracene described in step S3 is subjected to palladium-catalyzed Miyaura boronation reaction to obtain 2, 12-di-tert-butyl-7-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborinan-2-yl)-5, 9-dioxo-13B-” [3, 2, 1-DE] anthracene; S5, the 2, 2”, 6, 6”-tetrabromo-1, 1’: 4’, 1”-terphenyl described in step S1 is subjected to palladium-catalyzed Suzuki coupling reaction with the 2, 12-di-tert-butyl-7-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborinan-2-yl)-5, 9-dioxo-13B-” [3, 2, 1-DE] anthracene described in step S4 to obtain a reaction precursor compound; S6, under the action of the oxidant ferric trichloride, the reaction precursor compound described in step S5 is subjected to intramolecular oxidative dehydrogenation cyclization reaction, and the construction of double [7] helical chiral skeleton and the stable embedding of boron oxygen atom are realized at the same time, to obtain the peropyrene derivative expanded by the oxygen double [7] helical chiral skeleton.

[0010] In a third aspect, the present application also provides an organic electronic device comprising an active layer, wherein the active layer comprises the helical chiral peropyrene derivative described above.

[0011] The positive progress effect of the present application is that: This invention provides a helical chiral peropyrene derivative, its preparation method, and an organic electronic device. The helical chiral peropyrene derivative possesses a multi-helical chiral structure and boron-oxygen dual heteroatom doping, exhibiting excellent stability, moderate luminescence quantum efficiency, multi-site Lewis acidity, dynamic wavelength modulation of emission, circularly polarized luminescence performance, and reversible redox properties. The preparation method uses 2,2”,6,6”-tetrabromo-1,1':4',1”-terphenyl and 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene as precursors, synthesized via palladium-catalyzed coupling and an intramolecular oxidative dehydrogenation cyclization reaction initiated by ferric chloride. The preparation method is simple to operate and yields excellent results. The helical chiral peropyrene derivatives have broad application prospects in fields such as organic electronic devices, sensors, and smart response materials. Attached Figure Description

[0012] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1.

[0013] Figure 2 The single-crystal structure spectrum of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 is shown.

[0014] Figure 3 The UV-Vis absorption spectra of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 in different solvents.

[0015] Figure 4 The fluorescence emission spectra of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 in different solvents are shown.

[0016] Figure 5 The UV-Vis absorption spectrum of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1, obtained by chemical titration of tetrabutylammonium fluoride in tetrahydrofuran solvent.

[0017] Figure 6 The visible light emission spectrum of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1, obtained by chemical titration of tetrabutylammonium fluoride in tetrahydrofuran solvent.

[0018] Figure 7The cyclic voltammetry diagram of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 in dichloromethane solvent.

[0019] Figure 8 The circular dichroism absorption diagram of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 in dichloromethane solvent.

[0020] Figure 9 The circularly polarized emission spectrum of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 in dichloromethane solvent is shown. Detailed Implementation

[0021] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, specific embodiments of the present invention are described in detail below. It should be noted that the following embodiments are only used to illustrate the implementation methods and typical parameters of the present invention, and are not intended to limit the parameter range described in the present invention. Reasonable variations derived therefrom are still within the protection scope of the present invention.

[0022] It should be noted that the endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0023] Unless otherwise defined, all terms, symbols, and other scientific terms used herein are intended to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. In some instances, terms having a conventional meaning are defined herein for clarification or ease of reference, and such definitions should not be construed as indicating a significant difference from conventional understanding in the art. The technical methods described or referenced herein are generally well understood by those skilled in the art and employed by conventional methods. Unless otherwise stated, the use of commercially available kits, reagents, and instruments shall be performed according to the manufacturer's instructions and parameters.

[0024] The specific technical solution of this invention is as follows: In a first aspect, the present invention provides a helical chiral peropyrene derivative having a structure as shown in Formula I:

[0025] The helical chiral peropyrene derivative provided by this invention, through the synergistic effect of π-conjugated backbone, boron-oxygen heterocycle, tert-butyl substitution and double [7] helical chirality, possesses excellent stability, moderate luminescence quantum efficiency, multi-site Lewis acidity, dynamic modulation of luminescence wavelength, circularly polarized luminescence performance and reversible redox performance. The peropyrene core is a planar fused polycyclic aromatic hydrocarbon, combined with the twisted conjugated structure of the double [7] helix, which not only retains the chemical stability of the large π system, but also reduces the aggregation / degradation caused by intermolecular π-π stacking, thus improving solution and solid stability; the multiple tert-butyl groups on the periphery are sterically hindered groups, which prevent the contact between external active species and the conjugated backbone, thus improving chemical stability. The twisted structure of the double [7] helix destroys the complete planarity of the peropyrene core, so that the excited state is mainly relaxed through radiative transitions, thereby achieving moderate quantum efficiency; the boron-oxygen heterocycle makes the electron cloud distribution of the conjugated system more uniform, reduces the charge transfer quenching of the excited state, and maintains the luminescence efficiency. In helical chiral peropyrene derivatives, the boron atom in the boron-oxygen heterocycle provides multiple Lewis acid sites, allowing simultaneous interactions with multiple anions or solvent molecules, resulting in richer and more sensitive response signals. The empty orbitals of the boron atom in the boron-oxygen heterocycle can interact with solvents of different polarities / coordination, altering the electron cloud density of the conjugated system and thus modulating the energy of the π→π* transition, achieving dynamic control of the emission wavelength. The molecules of helical chiral peropyrene derivatives are not planar but possess both left-handed (M) and right-handed (P) helical enantiomeric chiral centers, causing the molecules to exhibit different efficiencies / responses to left-handed and right-handed circularly polarized light during excitation and emission. Therefore, when excited by ordinary light, helical chiral peropyrene derivatives can emit highly circularly polarized light. The large π-system of the peropyrene core stabilizes the charge after oxidation / reduction, while the B / O atoms disperse the charge generated during oxidation / reduction, making the redox process reversible. The helical twisted structure reduces irreversible aggregation caused by intermolecular charge transfer, further ensuring the reversibility of redox reactions.

[0026] Secondly, the present invention provides a method for preparing the above-mentioned helical chiral peropyrene derivative, comprising the following steps: S1, 1,3-dibromo-2-iodobenzene and 1,4-phenylenediboronic acid were coupled via a palladium-catalyzed Suzuki reaction to give 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl; S2, dibromo-1,4-difluorobenzene and 4-tert-butylphenol undergo an aromatic nucleophilic substitution reaction in the presence of potassium carbonate to give 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene); S3. The 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) described in step S2 undergoes a lithiation reaction with n-butyllithium to generate a lithium reagent, which then undergoes a stepwise reaction with boron tribromide. Specifically, the boron atom is first introduced into a specific site on the aromatic ring through an aromatic electrophilic substitution reaction, and then a six-membered boron-oxygen heterocyclic structure is constructed through a direct carbon-hydrogen bond boration reaction to obtain 7-bromo-2,12-ditert-butyl-5,9-dioxa-13B-boronnaphthalene[3,2,1-DE]anthracene. S4. The 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-bornaphthalene[3,2,1-DE]anthracene described in step S3 is subjected to a palladium-catalyzed Miyaura borylation reaction to obtain 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene; S5. The 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl described in step S1 and the 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene described in step S4 undergo a palladium-catalyzed Suzuki coupling reaction to obtain the precursor compound. S6. Under the action of the oxidant ferric chloride, the reaction precursor compound described in step S5 undergoes an intramolecular oxidative dehydrogenation cyclization reaction, simultaneously realizing the construction of the double [7] helical chiral framework and the stable insertion of boron-oxygen heteroatoms, to obtain peropyrene derivatives with extended double [7] helical chirality.

[0027] The method for preparing helical chiral peropyrene derivatives provided by this invention successfully integrates the three core functional units of helical chirality, boron-oxygen atoms, and large π-conjugated skeleton into one through a modular strategy of precursor construction (S1-S4), key fragment functionalization (S3), coupling (S5), and cyclization (S6). The two core precursors are prepared in parallel and independently, and finally key coupling is performed in step S5, which significantly improves the overall synthesis efficiency. In step S3, the directional introduction of boron atoms and the efficient construction of boron-oxygen heterocycles are achieved. This process has excellent regioselectivity and solves the key problem of accurately embedding boron and oxygen heteroatoms in complex fused ring skeletons. Step S6 uses ferric chloride as an intramolecular oxidative dehydrogenation cyclization reaction, which not only efficiently forms new carbon-carbon bonds and expands the π-conjugated system, but also simultaneously drives the linear precursor to twist and fold, and finally connects the double [7] helical chiral structure to the molecular skeleton, realizing the direct and efficient transformation from achiral precursors to chiral molecules.

[0028] In one possible implementation, step S1 specifically includes: adding the 1,3-dibromo-2-iodobenzene, the 1,4-phenylenediboric acid, a base reagent, and a palladium catalyst to a mixed solvent containing an organic solvent and water; after purging the atmosphere with nitrogen, heating to a set temperature for reaction; and after the reaction is completed, extraction, concentration, and column chromatography separation to obtain 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl. The use of a mixed solvent of organic solvent and water in step S1 is beneficial for improving the reaction rate and conversion rate of Suzuki coupling; the nitrogen-purged atmosphere completely eliminates oxygen in the system, ensuring the site selectivity of the coupling reaction; extraction with organic solvents such as ethyl acetate can efficiently separate the organic product from the inorganic salts in the aqueous phase, reducing impurity residues; concentration and column chromatography further purify the product to obtain high-purity 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl.

[0029] Furthermore, the mass ratio of 1,3-dibromo-2-iodobenzene to 1,4-phenylenediboronic acid is (4.3-5):1. In Suzuki coupling, the reactivity of the CI bond in 1,3-dibromo-2-iodobenzene is much higher than that of the C-Br bond. Using a mass ratio of (4.3-5):1 allows the two CB(OH)2 sites of 1,4-phenylenediboronic acid to preferentially cross-couple with the CI bond of 1,3-dibromo-2-iodobenzene, thereby generating 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl.

[0030] Further, the alkaline reagent is sodium bicarbonate, and the mass ratio of 1,4-phenylenediboric acid to sodium bicarbonate is 1:(2.89-3.0). The Suzuki coupling reaction requires a weakly alkaline environment, and the aqueous solution of sodium bicarbonate is weakly alkaline, perfectly matching the reaction requirements and ensuring the activation efficiency of boric acid. When the mass ratio is 1:(2.89-3.0), it ensures that boric acid is fully activated while maintaining the weakly alkaline stability of the system through excess sodium bicarbonate.

[0031] Furthermore, the mixed solvent is composed of dimethyl sulfoxide and water, with a volume ratio of dimethyl sulfoxide to water of (5-7):1. The mixture of dimethyl sulfoxide and water can simultaneously dissolve the substrate and the inorganic base, ensuring sufficient contact between the substrate, base, and catalyst within the same phase. At the limited volume ratio of (5-7):1, the high proportion of DMSO maintains the dissolution of the hydrophobic 1,3-dibromo-2-iodobenzene, while water ensures the dissociation of the base and the dissolution of 1,4-phenylenediboric acid. The synergistic effect of both ensures the homogeneity and stability of the reaction system.

[0032] Further, the palladium catalyst is a [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride dichloromethane complex, and the mass ratio of the catalyst to the 1,4-phenylenediboric acid is 1:(3.0-3.2). The reactivity of the CI bond in 1,3-dibromo-2-iodobenzene is much higher than that of the C-Br bond, and Pd(dppf)Cl2・CH2Cl2 can preferentially catalyze the cross-coupling of the CI bond with boric acid. When the mass ratio is 1:(3.0-3.2), it can be ensured that each boric acid group can effectively bind to the Pd(0) active center, promoting the reaction towards complete conversion.

[0033] Furthermore, the nitrogen replacement is carried out using nitrogen bubbling, with a bubbling time of 15-25 minutes; the set temperature is 60-70 °C, and the reaction time is 2-4 days. Nitrogen bubbling, by introducing nitrogen into the reaction liquid in the form of tiny bubbles, significantly increases the gas-liquid contact area, rapidly replacing oxygen and moisture in the system; the 15-25 minute time is sufficient to fully replace dissolved oxygen in the air and solvent within the reaction flask, ensuring the catalyst maintains high activity and preventing oxidation side reactions. 60-70 °C is the optimal temperature range for Pd(dppf)Cl2・CH2Cl2 catalyzed Suzuki coupling, which can activate the cross-coupling of CI bonds and boric acid, suppress side reactions, and ensure the structural regularity of the product.

[0034] Furthermore, the extraction reagent is ethyl acetate, and the extraction is performed 2-4 times. 2,2”,6,6”-Tetrabromo-1,1’:4’,1”-terphenyl is a hydrophobic aromatic compound with excellent solubility in ethyl acetate; while the byproducts in the reaction system (borate, excess sodium bicarbonate) are soluble in the aqueous phase, and ethyl acetate is immiscible with water, thus achieving efficient separation of organic phase products and aqueous phase impurities.

[0035] In one possible implementation, step S2 specifically includes: mixing the 2,5-dibromo-1,4-difluorobenzene, the 4-tert-butylphenol, an alkaline reagent, and an organic solvent under a nitrogen atmosphere, heating to a set temperature, and after the reaction, extracting, concentrating, and separating by column chromatography to obtain 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylphenol). The phenolic hydroxyl group of 4-tert-butylphenol needs to generate a phenoxy anion under alkaline conditions. However, the phenoxy anion is easily oxidized by oxygen to generate quinone byproducts. The nitrogen atmosphere can eliminate oxygen in the system, avoiding side reactions such as phenoxy anion oxidation and substrate degradation, ensuring the directional conduction of the nucleophilic substitution reaction. In 2,5-dibromo-1,4-difluorobenzene, the electron-withdrawing property of the F atom is stronger than that of the Br atom, which reduces the electron cloud density of the adjacent carbon atom. The phenoxy anion can precisely attack the carbon atom connected to the F atom to generate (4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene).

[0036] Furthermore, the mass ratio of 2,5-dibromo-1,4-difluorobenzene to 4-tert-butylphenol is 1:(1.6-1.7). This limited mass ratio of 1:(1.6-1.7) ensures that both F atoms of 2,5-dibromo-1,4-difluorobenzene are completely substituted, and also allows for the use of excess substrate to compensate for losses during the reaction process, thereby improving the conversion rate of the raw materials.

[0037] Further, the alkaline reagent is potassium carbonate, and the mass ratio of 2,5-dibromo-1,4-difluorobenzene to potassium carbonate is 1:(1.5-1.6). The phenolic hydroxyl group of 4-tert-butylphenol requires deprotonation under alkaline conditions to generate a phenoxide anion. The aqueous solution of potassium carbonate is weakly alkaline, and its alkalinity precisely matches the deprotonation requirement of the phenolic hydroxyl group, thus efficiently promoting the conversion of the phenolic hydroxyl group to the phenoxide anion while ensuring the directionality of the nucleophilic substitution reaction. When the mass ratio is 1:(1.5-1.6), the excess potassium carbonate ensures the presence of free CO3 in the system. 2- / HCO3 - The concentration is such that 4-tert-butylphenol is completely converted into phenol oxide anions.

[0038] Further, the organic solvent is anhydrous N-methylpyrrolidone, and the ratio of 2,5-dibromo-1,4-difluorobenzene to anhydrous N-methylpyrrolidone is 1 g:(4-5) mL. N-methylpyrrolidone can bind to hydrophobic groups through dipole-induced dipole interactions, achieving efficient dissolution of 2,5-dibromo-1,4-difluorobenzene and 4-tert-butylphenol. The strong polarity of N-methylpyrrolidone solubilizes potassium ions, promoting the dissociation of potassium carbonate and enabling homogeneous contact between the inorganic base and the organic substrate. 4-tert-butylphenol needs to be activated by potassium carbonate under anhydrous conditions to generate phenoxy anions. Anhydrous NMP eliminates moisture interference, ensuring the high nucleophilic activity of the phenoxy anions. The 1 g:(4-5) mL ratio ensures a sufficiently high concentration of both the organic substrate and the base, promoting intermolecular collisions without increasing system viscosity or hindering mass transfer due to excessive concentration.

[0039] Furthermore, the set temperature is 160-180 °C, and the reaction time is 18-22 h. The temperature of 160-180 °C significantly increases the molecular thermal motion rate, promoting effective collisions between the phenoxy anion and the electron-deficient carbon sites connected to the F atom in 2,5-dibromo-1,4-difluorobenzene. The substitution of the two F atoms in 2,5-dibromo-1,4-difluorobenzene is a stepwise process, and the 18-22 h reaction time ensures the complete completion of the second substitution reaction, increasing the yield of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene).

[0040] Furthermore, the extraction reagent is dichloromethane, and the extraction is performed 2-4 times. 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) is a hydrophobic aromatic compound with excellent solubility in dichloromethane. Impurities in the reaction system, such as excess potassium carbonate, potassium phenolate byproducts, and unreacted 4-tert-butylphenol, are all soluble in the aqueous phase. Since dichloromethane is immiscible with water, efficient separation of organic phase products from aqueous phase impurities can be achieved.

[0041] In one possible implementation, step S3 specifically includes: dissolving 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) in an organic solvent under a nitrogen atmosphere, performing a lithiation reaction, adding boron tribromide for a swelling reaction, then adding an organic amine reagent for a multi-stage temperature gradient reaction, and finally quenching, filtering, concentrating, and separating by column chromatography to obtain 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronaphthalene[3,2,1-DE]anthracene. The nitrogen atmosphere eliminates oxygen and moisture in the system, preventing quenching of the aryl lithium intermediate, hydrolysis of boron tribromide, and oxidation side reactions of the product, ensuring the directional conduction of the reaction. During the lithiation reaction, the Br atom in 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) exhibits strong electron-withdrawing properties. Through ortho-lithiation, it can directionally generate an aryllithium intermediate, providing a dedicated active center for the electrophilic substitution of boron atoms. During the expansion reaction, the aryllithium intermediate undergoes an electrophilic substitution reaction with boron tribromide, with the boron atom precisely binding to the lithiation-activated aromatic ring site, achieving the directional introduction of boron atoms. The addition of an organic amine reagent neutralizes the HBr generated in the reaction, adjusts the pH of the system, promotes the forward ring-closure reaction, and improves the formation efficiency and stability of the boron-oxygen heterocycle. The multi-stage temperature gradient reaction stabilizes the reaction intermediate between aryllithium and boron tribromide and promotes intramolecular boron-phenol-oxygen bonding, efficiently constructing a six-membered boron-oxygen heterocycle. The lithiation, boration, and multi-stage temperature gradient reactions are carried out in a one-pot process, eliminating the need to separate intermediates, simplifying the process, reducing intermediate losses, and improving overall synthesis efficiency.

[0042] Furthermore, the organic solvent is anhydrous m-xylene, and the ratio of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) to anhydrous m-xylene is 1 g:(9-11) mL. Anhydrous m-xylene eliminates interference from moisture, ensuring the reaction proceeds in a directed manner. As a nonpolar aromatic solvent, m-xylene achieves efficient dissolution of the substrate, ensuring a homogeneous reaction. The 1 g:(9-11) mL ratio ensures that the concentrations of both the substrate and reagent are sufficiently high to promote intermolecular collisions, while avoiding excessive concentrations that could increase system viscosity or hinder mass transfer.

[0043] Furthermore, the lithiation reaction is carried out at a temperature of -85 to -75 °C for 1.5 to 2.5 h. The low temperature environment of -85 to -75 °C can selectively activate the CH bonds adjacent to the Br atom, which is beneficial for achieving targeted lithiation at the target site. The reaction time of 1.5 to 2.5 h ensures that n-butyllithium reacts fully with the target CH bonds of the substrate, achieving complete lithiation.

[0044] Furthermore, the reagent used in the lithiation reaction is 1.2-2 mol / L n-butyllithium, and the ratio of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) to n-butyllithium is 1 g:(1.1-1.2) mL. The 1.2-2 mol / L concentration of n-butyllithium is suitable for the solubility of the low-temperature system, ensuring uniform mixing of n-butyllithium and the substrate and avoiding non-selective lithiation caused by localized uneven concentration. The ratio of 1 g:(1.1-1.2) mL ensures complete lithiation of the target CH bonds of the substrate.

[0045] Further, the concentration of boron tribromide is 1.6-2.5 mol / L, and the ratio of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) to boron tribromide is 1 g:(1.0-1.2) mL. The concentration of boron tribromide at 1.6-2.5 mol / L ensures uniform mixing of boron tribromide and the aryllithium intermediate. The ratio of 1 g:(1.0-1.2) mL ensures complete conversion of the aryllithium intermediate to the borate intermediate, which is beneficial for the complete completion of the subsequent ring-closing reaction.

[0046] Furthermore, the initial temperature of the borylation reaction is -85 to -75 °C, and the reaction time is 0.8 to 1.2 h. After returning to room temperature for 25 to 35 min, the temperature is then raised to 40 to 50 °C for another 0.8 to 1.2 h. The low temperature environment of -85 to -75 °C locks the active center of the aryl lithium intermediate, causing it to undergo a directional electrophilic substitution reaction only with the electron-deficient B atom of boron tribromide, achieving precise insertion of the boron atom. The reaction time of 0.8 to 1.2 h at -85 to -75 °C ensures complete reaction between the aryl lithium intermediate and boron tribromide. The room temperature transition allows for a slow release of the reaction heat within the system, enabling the intermediate to gradually adapt to temperature changes and avoiding structural damage caused by thermal stress. The temperature of 40 to 50 °C provides the activation energy required for intramolecular B-phenol-oxygen bonding, promoting intramolecular nucleophilic substitution reactions between the B-Br bond in the borylation intermediate and the ortho-phenol-oxygen atom, gradually forming a six-membered boron-oxygen heterocycle, achieving directional and efficient construction of the heterocycle. Reacting at 40-50 ℃ for 0.8-1.2 h ensures that all borylation intermediates complete the ring-closing reaction, guaranteeing the structural integrity and uniformity of the boron-oxygen heterocycles in the target product.

[0047] Further, the organic amine reagent is N,N-diisopropylethylamine, and the molar ratio of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) to N,N-diisopropylethylamine is 1 g:(0.6-0.7) mL. N,N-diisopropylethylamine can neutralize the HBr generated during the borylation and ring-closing reactions. The 1 g:(0.6-0.7) mL molar ratio ensures complete neutralization of HBr, preventing residual HBr from catalyzing the hydrolysis of the boron-oxygen heterocycle and preserving the integrity of the heterocycle structure.

[0048] Furthermore, the multi-stage temperature gradient reaction includes: after the borylation reaction, the temperature is first lowered to 0-5 °C, the organic amine reagent is added, and the reaction time after returning to room temperature is 25-35 min. Finally, the temperature is raised to 130-140 °C and reacted for 18-22 h. At the low temperature of 0-5 °C, the activity of boron tribromide decreases, and the organic amine preferentially reacts with HBr, ensuring the purity of the borylation intermediate and reserving active sites for subsequent ring-closing reactions. The buffer stage of raising the temperature from 0-5 °C to room temperature can prevent conformational disorder or structural damage of the borylation intermediate due to thermal shock, ensuring the structural integrity of the intermediate. The 25-35 min time can ensure complete conformational adjustment. The formation of the six-membered boron-oxygen heterocycle (-OB-) requires the breaking of the B-Br bond. The high temperature of 130-140 °C provides sufficient activation energy to promote intramolecular nucleophilic substitution reaction of the borylation intermediate, efficiently constructing a stable six-membered boron-oxygen heterocycle. Intramolecular ring-closing reactions are slow reactions, and a long reaction time of 18-22 hours can ensure that the intermediate completes the ring closure.

[0049] Furthermore, the quenching agent is methanol. Methanol can neutralize residual n-butyllithium, aryl intermediates, and boron tribromide in the reaction system, preventing side reactions and eliminating safety hazards during subsequent processing.

[0050] In one possible implementation, step S4 specifically includes: adding the 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-borona[3,2,1-DE]anthracene, pinacol diborate, a base reagent, and a palladium catalyst to an organic solvent; after purging the atmosphere with nitrogen, heating to a set temperature for reaction; and after the reaction is completed, extraction, concentration, and column chromatography are performed to obtain 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxa-13B-borona[3,2,1-DE]anthracene. Nitrogen purging removes oxygen and moisture from the system, preventing deactivation of the palladium catalyst and degradation of the boron reagent, and ensuring the directional conduction of the borylation reaction. The C-Br bond in the substrate 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronaphthyl[3,2,1-DE]anthracene is the specific reaction site for Miyaura borylation. Pinacol diboronate, as a mild boron source, can precisely introduce a boron ester group (-Bpin) to the Br site under palladium catalysis. A basic reagent can activate pinacol diboronate, generating an active boron species, promoting the "transmetallization" step in the palladium catalytic cycle, and increasing the reaction rate. Organic solvents can dissolve all reaction components, ensuring homogeneous reaction and avoiding incomplete reactions caused by mass transfer barriers.

[0051] Furthermore, the mass ratio of the 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-borona[3,2,1-DE]anthracene to the pinacol diboronate is 1:(0.8-0.9). This mass ratio of 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-borona[3,2,1-DE]anthracene to pinacol diboronate promotes the reversible Miyaura borylation reaction in the forward direction, ensuring complete conversion of the Br-containing substrate.

[0052] Further, the base reagent is potassium acetate, and the mass ratio of 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronaphthalene[3,2,1-DE]anthracene to potassium acetate is 1:(2.0-2.2). Potassium acetate, as a weakly basic inorganic base, can undergo a coordination reaction with pinacol diboronate to generate a moderately nucleophilic active boron species, which can rapidly undergo a transmetallization reaction with the palladium catalytic intermediate, significantly improving catalytic cycle efficiency and shortening reaction time. Limiting the mass ratio to 1:(2.0-2.2) allows for precise control of the base concentration, selectively activating the boron reagent and catalytic cycle, driving the reversible Miyaura borylation reaction forward, and ensuring complete conversion of 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronaphthalene[3,2,1-DE]anthracene.

[0053] Further, the organic solvent is 1,4-dioxane, and the molar ratio of 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronaphthalene[3,2,1-DE]anthracene to 1,4-dioxane is 1 g:(45-55) mL. 1,4-dioxane can combine with the aromatic ring through hydrophobic interactions, dissolving the hydrophobic substrate 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronaphthalene[3,2,1-DE]anthracene; simultaneously, the ether bond of 1,4-dioxane can form a weak coordination with the boron reagent and catalyst, promoting the dissolution of pinacol diborate. The molar ratio of 1 g:(45-55) mL ensures that the concentrations of the substrate, boron reagent, and catalyst are sufficiently high to promote intermolecular collisions, while avoiding excessive concentration leading to increased system viscosity and hindered mass transfer.

[0054] Further, the palladium catalyst is 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride, and the mass ratio of the palladium catalyst to the 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronaphthalene[3,2,1-DE]anthracene is 1:(20-22). The bisphosphine structure of the 1,1'-bis(diphenylphosphine)ferrocene ligand in the 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride stabilizes the catalytic cycle intermediate and possesses moderate electron-donating ability, which can significantly enhance the oxidative addition activity of the Pd center to aryl bromides, rapidly start the catalytic cycle, and shorten the reaction time. The limited mass ratio of 1:(20-22) provides sufficient catalyst to overcome the steric hindrance of the tert-butyl and boron-oxygen heterocycles in the substrate structure, ensuring effective contact between the substrate molecule and the catalytic center.

[0055] Furthermore, the extraction reagent is dichloromethane, and the extraction is performed 2-4 times. Dichloromethane can efficiently bind to aromatic rings through hydrophobic interactions, achieving rapid dissolution of 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-borona[3,2,1-DE]anthracene; while impurities in the reaction system (excess potassium acetate, potassium bromide, palladium catalyst residue, and pinacol ester hydrolysis products of diboronate) are readily soluble in the aqueous phase, and dichloromethane is completely immiscible with water, enabling precise stratification of the organic phase product and the aqueous phase impurities. 2-4 extractions can improve product recovery and purity.

[0056] In one possible implementation, step S5 specifically includes: adding the 2,2”,6,6”-tetrabromo-1,1':4',1”-terphenyl and the 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-bornaphthalene[3,2,1-DE]anthracene, a base reagent, and a palladium catalyst to a mixed solvent consisting of an organic solvent and water. After purging the atmosphere with nitrogen, the mixture is heated to a set temperature to carry out a Suzuki coupling reaction. After the reaction, the precursor compound is obtained by extraction, concentration, and column chromatography. Using a mixed system of organic solvent and water allows the hydrophobic substrate and palladium catalyst to dissolve in the organic phase, while the base reagent dissolves in the aqueous phase, forming a stable reaction system. Nitrogen purging removes oxygen from the system, maintaining the catalyst's sustained high activity. Tetrabromo-1,1':4',1”-terphenyl serves as the core framework of a tetrafunctional group, with its Br atoms at the 2,2”,6,6” positions exhibiting equal reactivity. 2,12-Di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-borona[3,2,1-DE]anthracene) acts as an electrophilic coupling pair, precisely replacing the Br atoms of the terphenyl via the Suzuki reaction to form a symmetrical precursor structure with a terphenyl core and four boron-oxygen heterocyclic side chains. The palladium catalyst activates only the cross-coupling of the C-Br and BO bonds, without attacking other functional groups in the substrate, ensuring the symmetry and regularity of the precursor structure and laying the spatial basis for subsequent helical chirality. The alkaline reagent neutralizes the HBr generated in the reaction, maintaining an alkaline environment in the system.

[0057] Furthermore, the mass ratio of the 2,2”,6,6”-tetrabromo-1,1':4',1”-terphenyl to the 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-boronaphthyl[3,2,1-DE]anthracene is 1:(7.0-7.5). This specific mass ratio of 1:(7.0-7.5) drives the reversible Suzuki coupling reaction in the forward direction, ensuring complete substitution of all Br sites.

[0058] Further, the alkaline reagent is potassium carbonate, and the mass ratio of 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl to potassium carbonate is 1:(3.8-4.0). Potassium carbonate can undergo a coordination-deprotonation reaction with boron ester groups to generate an active boron species, which can rapidly undergo a transmetallization reaction with palladium catalytic intermediates, improving catalytic cycle efficiency. The limited mass ratio of 1:(3.8-4.0) can promote the reversible Suzuki coupling reaction to the forward direction and suppress the occurrence of side reactions.

[0059] Furthermore, the mixed solvent is composed of 1,4-dioxane and water, with a volume ratio of 1,4-dioxane to water of (5-7):1. 1,4-dioxane can dissolve the substrate, and water can efficiently dissolve the base reagent, forming a homogeneous alkaline environment that promotes the activation reaction of potassium carbonate and boronic ester groups. The limited volume ratio of (5-7):1 ensures both efficient dissolution of the hydrophobic substrate and the palladium catalyst, while also meeting the dissolution requirements of potassium carbonate, thus achieving homogeneous contact between the inorganic base and the organic substrate.

[0060] Furthermore, the ratio of the 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl to the mixed solvent is 1 g:(120-130) mL. Limiting the ratio to 1 g:(120-130) mL ensures, on the one hand, complete dissolution of the hydrophobic substrate (tetrabromo-terphenyl, boron ester substrate) and uniform dispersion of potassium carbonate in the mixed solvent; on the other hand, it provides sufficient space for contact between the substrate molecules and the catalytic center, ensuring that all four Br sites can participate efficiently in the reaction.

[0061] Furthermore, the palladium catalyst is tetratetraphenylphosphine palladium, and the mass ratio of the palladium catalyst to 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl is 1:(3.7-3.9). The triphenylphosphine ligand of tetratetraphenylphosphine palladium has excellent activation ability for large-volume aryl bromides, which can efficiently overcome steric hindrance and ensure that the four Br sites are coupled sequentially; when the mass ratio is 1:(3.7-3.9), sufficient catalyst can ensure that each Br site can fully contact the palladium active species.

[0062] Furthermore, the nitrogen replacement is performed using nitrogen bubbling, with a bubbling time of 15-25 minutes. Nitrogen bubbling, by introducing nitrogen in the form of tiny bubbles into the 1,4-dioxane-water mixture, significantly increases the gas-liquid contact area, enabling rapid and thorough replacement of oxygen and moisture in the system. The 15-25 minute time ensures effective impurity removal and provides a stable inert environment for the four-site coupling reaction.

[0063] Furthermore, the set temperature is 95-105 °C; the Suzuki coupling reaction time is 22-26 h. The temperature range of 95-105 °C provides sufficient activation energy, improving the activation efficiency of the palladium catalyst for the C-Br bond and ensuring that the four Br sites are coupled sequentially and efficiently. The four-site coupling reaction is stepwise, requiring sufficient time to ensure complete conversion of all sites; the 22-26 h time range ensures the stepwise reaction is completed.

[0064] Furthermore, the extraction reagent is dichloromethane, and the extraction is performed 2-4 times. Dichloromethane, as a moderately polar halogenated hydrocarbon solvent, can efficiently bind to aromatic ring structures through hydrophobic interactions, achieving rapid and complete dissolution of the product. Meanwhile, the impurities in the reaction system (excess potassium carbonate, potassium bromide, Pd(PPh3)4 catalyst residue, and boron ester hydrolysis products) are all water-soluble or polar compounds. Dichloromethane is completely immiscible with water, enabling precise stratification of the organic phase product and the aqueous phase impurities. 2-4 extractions can improve product recovery and purity.

[0065] In one possible implementation, step S6 specifically includes: dissolving the reaction precursor compound in a dry organic solvent, purging the atmosphere with nitrogen, adding a ferric chloride nitromethane solution dropwise under refrigeration and temperature control, sealing and stirring to carry out an intramolecular oxidative dehydrogenation cyclization reaction, and after the reaction is completed, quenching, filtering, and column chromatography to obtain the peropyrene derivative with extended boron-oxygen heterocycle chirality [7]. Using a dry organic solvent can remove moisture, avoid the hydrolysis of ferric chloride to generate ferric hydroxide precipitate which would lead to deactivation of the oxidant, and at the same time prevent the boron-oxygen heterocycle in the product from undergoing hydrolysis and breakage; at the same time, the organic solvent can efficiently dissolve the reaction precursor and the ferric chloride nitromethane solution, ensuring that the reaction proceeds homogeneously. Nitrogen purging can completely remove oxygen from the system, ensuring the directional progress of the oxidative dehydrogenation cyclization reaction, and at the same time protecting the generated helical chiral structure from being oxidized and destroyed. Intramolecular oxidative dehydrogenation cyclization is an exothermic reaction, and the precursor contains multiple potential cyclization sites. Low-temperature environments can enhance reaction selectivity, ensuring that the cyclization reaction occurs only at the predetermined ortho position of the aromatic ring, avoiding chiral isomer mixtures or structurally defective products caused by random cyclization. Ferric chloride can selectively oxidize the CH bond of the aromatic ring in the precursor, initiating an intramolecular free radical cyclization reaction to form a new C-C bond; nitromethane (CH3NO2), as a strongly polar, protically inert solvent, can react with Fe through the lone pair electrons of the nitro group. 3+ A stable coordination compound (FeCl3・nCH3NO2) is formed, releasing mononuclear Fe. 3+ The active species significantly enhances the dehydrogenation ability of the CH bond within the precursor molecule, accelerates the formation of aryl radical intermediates, and promotes the rate of intramolecular cyclization reaction. The addition of a ferric chloride-nitromethane solution allows for precise control of the oxidant concentration, ensuring the orderly and stepwise execution of the "dehydrogenation-cyclization" process and preserving the regularity and symmetry of the helical chiral skeleton.

[0066] Furthermore, the organic solvent is dichloromethane, and the molar ratio of the precursor compound to dichloromethane is 1 g:(550-600) mL. This molar ratio of 1 g:(550-600) mL maximizes the dispersion of the precursor molecules, reduces intermolecular interactions, and provides ample space for intramolecular radical coupling at the ortho position of the aromatic ring, promoting the directional "intramolecular dehydrogenation-cyclization" process and suppressing intermolecular side reactions.

[0067] Furthermore, the mass ratio of the precursor compound to the ferric chloride is 1:(5.5-5.6). When the mass ratio of the precursor compound to ferric chloride is 1:(5.5-5.6), ferric chloride can rapidly abstract electrons from the target CH bond within the precursor molecule to generate aryl radicals, promoting rapid cyclic closure of the intramolecular radicals.

[0068] Furthermore, the ratio of ferric chloride to nitromethane is 1 g:(11-12) mL. When the ratio of ferric chloride to nitromethane is 1 g:(11-12) mL, sufficient nitromethane can achieve adequate coordination of FeCl3, ensuring that all FeCl3 is converted into active species.

[0069] Furthermore, the temperature for the cooling and temperature control is -5 to 5 °C. The core competition in the intramolecular oxidative dehydrogenation cyclization reaction is the intramolecular radical cyclization and the intermolecular radical coupling. The low temperature environment of -5 to 5 °C can significantly reduce the diffusion rate and collision probability of radical intermediates, making the intramolecular reaction the thermodynamically dominant pathway. At the same time, the low temperature can prolong the lifetime of radical intermediates, providing sufficient time for intramolecular multi-step cyclization and ensuring that the cyclization reaction proceeds in a step-by-step and orderly manner.

[0070] Furthermore, the intramolecular oxidative dehydrogenation cyclization reaction takes 25-35 minutes. This 25-35 minute reaction time ensures complete dehydrogenation of the eight pre-defined CH bonds within the precursor molecule, and completes the two helical ring-closing reactions.

[0071] Furthermore, the quenching agent is methanol. The hydroxyl hydrogen of methanol can undergo a proton transfer reaction with the residual aryl radical intermediate in the system to generate a stable aromatic ring compound. At the same time, methanol is converted into a methoxy radical, blocking subsequent side reactions initiated by the radical.

[0072] Thirdly, the present invention provides an organic electronic device comprising an active layer, the active layer comprising the above-mentioned helical chiral peropyrene derivative.

[0073] The technical solution of the present invention will be further described below with reference to specific embodiments and comparative examples. All reagents used in the embodiments are commercially available or synthesized by conventional methods and can be used directly without further processing. The instruments used in the embodiments are also commercially available.

[0074] Example 1 This embodiment provides a helical chiral peropyrene derivative, which is prepared by the following steps: S1. In a Shrek reaction flask, add 1.4 g of 1,3-dibromo-2-iodobenzene, 323 mg of 1,4-phenylenediboric acid, 934 mg of sodium bicarbonate, 60 mL of dimethyl sulfoxide, and 10 mL of water. Bubble the mixture in the flask with nitrogen for 20 min. Add 105 mg of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride dichloromethane complex to the mixture. Heat the mixture to 65 °C and react for 3 days. After the reaction is complete, restore the product solution to room temperature, pour it into water, and extract it three times with ethyl acetate. Collect the organic phase. Concentrate the organic phase by vacuum distillation and separate it by column chromatography to obtain 311 mg of 2,2'',6,6''-tetrabromo-1,1':4',1''-terphenyl, a white powder solid with a yield of 29%. The specific synthetic route is shown in Formula II. (II); S2. Under a nitrogen atmosphere, 10 g of 2,5-dibromo-1,4-difluorobenzene, 16.6 g of 4-tert-butylphenol, 15.3 g of potassium carbonate, and 45 mL of anhydrous N-methylpyrrolidone were added to a Shrek reaction flask. The mixture in the flask was heated to 170 °C and reacted for 20 hours. After the reaction was completed, the reaction product solution was brought to room temperature, poured into water, and extracted three times with dichloromethane. The organic phase was collected. The organic phase was concentrated by vacuum distillation, and 16 g of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) was obtained by column chromatography as a white solid with a yield of 87%. The specific synthetic route is shown in Formula III. (III); S3. Under a nitrogen atmosphere, add 4 g of the 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) and 40 mL of anhydrous m-xylene to a Shrek reaction flask. Cool the mixture in the flask to -80 °C, add 4.68 mL of 1.5 mol / L n-butyllithium, and react for 2 hours. Continue to add 4.5 mL of 2 mol / L boron tribromide, and react for 1 hour. Return to room temperature and continue reacting for 30 minutes. Raise the temperature to 45 °C and react for 1 hour. Cool to 0 °C, add 2.5 mL of N,N-diisopropylethylamine, return to room temperature and react for 30 minutes. Raise the temperature to 135 °C. The reaction was carried out at ℃ for 20 hours. After the reaction was completed, the product solution was brought back to room temperature, methanol was added to quench the reaction, and the organic phase was collected by filtration. The organic phase was concentrated by vacuum distillation, and 1.9 g of 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronaphthalene[3,2,1-DE]anthracene was obtained by column chromatography as a white solid with a yield of 54%. The specific synthetic route is shown in Formula IV. (IV); S4. In a Shrek reaction flask, add 1.0 g of the stated 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-borona[3,2,1-DE]anthracene, 829 mg of pinacol diborate, 2.1 g of potassium acetate, and 50 mL of 1,4-dioxane. Bubble the mixture in the flask with nitrogen for 20 minutes. Add 47.6 mg of 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride to the mixture and heat the mixture to 110°C. The reaction was carried out at ℃ for 12 hours. After the reaction, the product solution was brought back to room temperature, poured into water, and extracted three times with dichloromethane. The organic phase was collected. The organic phase was concentrated by vacuum distillation and separated by column chromatography to obtain 993 mg of 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene, a white solid with a yield of 90%. The specific synthetic route is shown in Formula V. (V); S5. In a Shrek reaction flask, add 164 mg of 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl obtained in step S1 and 1.2 g of the 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”-[3,2,1-DE]anthracene obtained in step S4, 640 mg of potassium carbonate, 21 mL of 1,4-dioxane, and 3 mL of water. Bubble the mixture in the flask with nitrogen for 20 minutes. Add 43.3 mg of tetrakis(triphenylphosphine)palladium to the mixture and heat the mixture to 100°C. The reaction was carried out at ℃ for 15 hours. After the reaction, the product solution was brought back to room temperature, poured into water, and extracted three times with dichloromethane. The organic phase was collected. The organic phase was concentrated by vacuum distillation, and 275 mg of the precursor compound, designated TP-4BO, was obtained by column chromatography. The precursor was a white powder with a yield of 53%. The specific synthetic route is shown in Formula VI. (VI); S6. Add 170 mg of the reaction precursor compound TP-4BO prepared in step S5 and 97 mL of dry dichloromethane to a 50 mL Shrek reaction flask, and bubble the mixture in the flask with nitrogen for 20 minutes; dissolve 944 mg of ferric chloride in 11 mL of nitromethane, and slowly add it dropwise to the above compound at 0 °C; after the addition is complete, under sealed conditions, continue to stir the entire reaction system with a magnetic stirrer at 0 °C for 30 minutes; add methanol to the reaction system, filter and collect the precipitate, and separate 119 mg of the peropyrene derivative with double [7] helical chirality by column chromatography, denoted as [7]BO-PP, a brick-red powder solid with a yield of 70%. The specific synthetic route is shown in Formula VII: (VII)

[0075] Example 2 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S1. In a Shrek reaction flask, add 1.515 g of 1,3-dibromo-2-iodobenzene, 323 mg of 1,4-phenylenediboric acid, 969 mg of sodium bicarbonate, 70 mL of dimethyl sulfoxide, and 10 mL of water. Bubble the mixture in the flask with nitrogen for 25 min. Add 104.3 mg of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride dichloromethane complex to the mixture. Heat the mixture to 70 °C and react for 2 days. After the reaction is complete, restore the product solution to room temperature, pour it into water, and extract it three times with ethyl acetate. Collect the organic phase. Concentrate the organic phase by vacuum distillation and separate it by column chromatography to obtain 318 mg of 2,2'',6,6''-tetrabromo-1,1':4',1''-terphenyl, a white powder solid, with a yield of 30%. Everything else is the same as in Example 1.

[0076] Example 3 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S1. In a Shrek reaction flask, add 1.453 g of 1,3-dibromo-2-iodobenzene, 322 mg of 1,4-phenylenediboric acid, 934 mg of sodium bicarbonate, 50 mL of dimethyl sulfoxide, and 10 mL of water. Bubble the mixture in the flask with nitrogen for 15 min. Add 101 mg of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride dichloromethane complex to the mixture. Heat the mixture to 65 °C and react for 3 days. After the reaction is complete, restore the product solution to room temperature, pour it into water, and extract it three times with ethyl acetate. Collect the organic phase. Concentrate the organic phase by vacuum distillation and separate it by column chromatography to obtain 313 mg of 2,2'',6,6''-tetrabromo-1,1':4',1''-terphenyl, a white powder solid, with a yield of 29.5%. Everything else is the same as in Example 1.

[0077] Example 4 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S2. Under a nitrogen atmosphere, 10 g of 2,5-dibromo-1,4-difluorobenzene, 17 g of 4-tert-butylphenol, 16 g of potassium carbonate, and 50 mL of anhydrous N-methylpyrrolidone were added to a Shrek reaction flask. The mixture in the flask was heated to 180 °C and reacted for 18 hours. After the reaction was completed, the reaction product solution was brought to room temperature, poured into water, and extracted three times with dichloromethane. The organic phase was collected. The organic phase was concentrated by vacuum distillation, and 15.8 g of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) was obtained by column chromatography as a white solid with a yield of 86%. Everything else is the same as in Example 1.

[0078] Example 5 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S2. Under a nitrogen atmosphere, 10 g of 2,5-dibromo-1,4-difluorobenzene, 16 g of 4-tert-butylphenol, 15 g of potassium carbonate, and 40 mL of anhydrous N-methylpyrrolidone were added to a Shrek reaction flask. The mixture in the flask was heated to 160 °C and reacted for 22 hours. After the reaction was completed, the reaction product solution was brought to room temperature, poured into water, and extracted three times with dichloromethane. The organic phase was collected. The organic phase was concentrated by vacuum distillation, and 15.8 g of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) was obtained by column chromatography as a white solid with a yield of 84%. Everything else is the same as in Example 1.

[0079] Example 6 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S3. Under a nitrogen atmosphere, add 4 g of the 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) and 44 mL of anhydrous m-xylene to a Shrek reaction flask. Cool the mixture in the flask to -85 °C, add 4.8 mL of 1.5 mol / L n-butyllithium, and react for 1.5 hours. Continue to add 4.8 mL of 2.5 mol / L boron tribromide, and react for 1 hour. Return to room temperature and continue reacting for 25 minutes. Raise the temperature to 50 °C and react for 1 hour. Cool to 5 °C, add 2.8 mL of N,N-diisopropylethylamine, return to room temperature and react for 25 minutes. Raise the temperature to 140 °C. The reaction was carried out at ℃ for 18 hours. After the reaction was completed, the product solution was brought back to room temperature, methanol was added to quench the reaction, and the organic phase was collected by filtration. The organic phase was concentrated by vacuum distillation, and 1.82 g of 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronaphthalene[3,2,1-DE]anthracene was obtained by column chromatography as a white solid with a yield of 51%. Everything else is the same as in Example 1.

[0080] Example 7 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S3. Under a nitrogen atmosphere, add 4 g of the 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) and 36 mL of anhydrous m-xylene to a Shrek reaction flask. Cool the mixture in the flask to -75 °C, add 4.4 mL of 1.2 mol / L n-butyllithium, and react for 2.5 h. Continue to add 4 mL of 1.6 mol / L boron tribromide, and react for 1.2 h. Return to room temperature and continue reacting for 35 min. Raise the temperature to 40 °C and react for 1 h. Cool to 0 °C, add 2.4 mL of N,N-diisopropylethylamine, return to room temperature and react for 35 min. Raise the temperature to 130 °C. The reaction was carried out at ℃ for 22 hours. After the reaction was completed, the product solution was brought back to room temperature, methanol was added to quench the reaction, and the organic phase was collected by filtration. The organic phase was concentrated by vacuum distillation and separated by column chromatography to obtain 1.78 g of 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronaphthalene[3,2,1-DE]anthracene, a white solid with a yield of 50%. Everything else is the same as in Example 1.

[0081] Example 8 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S4. In a Shrek reaction flask, add 1.0 g of the stated 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-borona[3,2,1-DE]anthracene, 900 mg of pinacol diborate, 2.2 g of potassium acetate, and 55 mL of 1,4-dioxane. Bubble the mixture in the flask with nitrogen for 20 minutes. Add 47.6 mg of 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride to the mixture and heat the mixture to 110°C. The reaction was carried out at ℃ for 12 hours. After the reaction was completed, the product solution was brought to room temperature, poured into water, and extracted four times with dichloromethane. The organic phase was collected. The organic phase was concentrated by vacuum distillation and separated by column chromatography to obtain 995 mg of 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene, a white solid with a yield of 90%. Everything else is the same as in Example 1.

[0082] Example 9 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S4. In a Shrek reaction flask, add 1.0 g of the stated 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-borona[3,2,1-DE]anthracene, 800 mg of pinacol diborate, 2 g of potassium acetate, and 45 mL of 1,4-dioxane. Bubble the mixture in the flask with nitrogen for 15 minutes. Add 45.5 mg of 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride to the mixture and heat the mixture to 110°C. The reaction was carried out at ℃ for 12 hours. After the reaction was completed, the product solution was brought to room temperature, poured into water, and extracted twice with dichloromethane. The organic phase was collected. The organic phase was concentrated by vacuum distillation and separated by column chromatography to obtain 970 mg of 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene, a white solid with a yield of 88%. Everything else is the same as in Example 1.

[0083] Example 10 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S5. In a Shrek reaction flask, add 164 mg of 2,2”,6,6”-tetrabromo-1,1”:4”,1”-terphenyl obtained in step S1 and 1.148 g of the 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene obtained in step S4, 1.6 g of potassium carbonate, 17 mL of 1,4-dioxane, and 3 mL of water. Bubble the mixture in the flask with nitrogen for 25 minutes. Add 108.1 mg of tetra-triphenylphosphine palladium to the mixture and heat the mixture to 105 °C. The reaction was carried out at ℃ for 22 hours. After the reaction was completed, the product solution was brought to room temperature, poured into water, and extracted three times with dichloromethane. The organic phase was collected. The organic phase was concentrated by vacuum distillation, and 250 mg of the precursor compound, designated TP-4BO, was obtained by column chromatography. The precursor compound was a white powder with a yield of 48%. Everything else is the same as in Example 1.

[0084] Example 11 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S5. In a Shrek reaction flask, add 164 mg of 2,2”,6,6”-tetrabromo-1,1”:4”,1”-terphenyl obtained in step S1 and 1.230 g of the 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene obtained in step S4, 1.6 g of potassium carbonate, 18.5 mL of 1,4-dioxane, and 3 mL of water. Bubble the mixture in the flask with nitrogen for 25 minutes. Add 108.1 mg of tetraphenylphosphine palladium to the mixture and heat the mixture to 105 °C. The reaction was carried out at ℃ for 22 hours. After the reaction was completed, the product solution was brought to room temperature, poured into water, and extracted three times with dichloromethane. The organic phase was collected. The organic phase was concentrated by vacuum distillation, and 265 mg of the precursor compound, designated TP-4BO, was obtained by column chromatography. The precursor compound was a white powder with a yield of 51%. Everything else is the same as in Example 1.

[0085] Example 12 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S6. Add 170 mg of the reaction precursor compound TP-4BO prepared in step S5 and 96 mL of dry dichloromethane to a 50 mL Shrek reaction flask, and bubble the mixture in the flask with nitrogen for 20 minutes; dissolve 935 mg of ferric chloride in 10.3 mL of nitromethane, and slowly add it dropwise to the above compound at 0 °C; after the addition is complete, under sealed conditions, continue to stir the entire reaction system with a magnetic stirrer at 0 °C for 25 minutes; add methanol to the reaction system, filter and collect the precipitate, and separate 110 mg of the peropyrene derivative with double [7] helical chiral extension by column chromatography, brick red powder solid, with a yield of 65%; Everything else is the same as in Example 1.

[0086] Example 13 This embodiment provides a helical chiral peropyrene derivative, the preparation steps of which differ from those in Example 1: S6. Add 170 mg of the reaction precursor compound TP-4BO prepared in step S5 and 98 mL of dry dichloromethane to a 50 mL Shrek reaction flask, and bubble the mixture in the flask with nitrogen for 20 minutes; dissolve 952 mg of ferric chloride in 11.4 mL of nitromethane, and slowly add it dropwise to the above compound at 0 °C; after the addition is complete, under sealed conditions, continue to stir the entire reaction system with a magnetic stirrer at 0 °C for 35 minutes; add methanol to the reaction system, filter and collect the precipitate, and separate 120 mg of the peropyrene derivative with double [7] helical chiral extension by column chromatography, brick red powder solid, with a yield of 71%; Everything else is the same as in Example 1.

[0087] Performance Testing and Result Analysis The helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 was subjected to 1H NMR spectroscopy, single crystal structure, UV-Vis absorption spectroscopy, fluorescence emission spectroscopy, cyclic voltammetry, circular dichroism absorption and circular polarization emission spectroscopy. The test results are as follows: Figure 1The 1H NMR spectrum of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 is as follows: 1H NMR (600 MHz, CD2Cl2): δ (ppm) = 9.61 (d, J = 7.9 Hz, 4H), 8.72 (s, 4H), 8.58 (t, J = 7.6 Hz, 2H), 8.50 (s, 4H), 8.38 (s, 4H), 7.72 (d, J = 8.8 Hz, 4H), 7.47 (d, J = 8.9 Hz, 4H), 7.44 (d, J = 8.6 Hz, 4H), 6.51 (d, J = 8.8 Hz, 4H), 1.37 (s, 36H), 1.31 (s, 36H). The region δ 9.61–8.50 ppm belongs to the core Peropyrene skeleton and the hydrogen atoms on other aromatic rings directly fused with it. Due to the molecule's large π-conjugation system and electron-deficient characteristics, these protons experience weak shielding effects, resulting in a lower chemical shift. The multiple sharp singlets, doublets, and triplets in this region precisely reflect the specific symmetry of the large Peropyrene molecule. The region δ 6.25 ppm likely belongs to protons on the benzene ring directly bonded to the oxygen atom (i.e., hydrogen atoms on the benzene ring bonded to the tert-butyl group). The lone pair electrons of the oxygen atom donate electrons to the benzene ring through conjugation, increasing the electron cloud density around these protons and subjecting them to a stronger shielding effect. Therefore, the chemical shift moves to a higher field, which is significantly different from ordinary benzene ring protons (δ ~7.3 ppm). This directly proves the existence of the boron-oxygen heterocycle structure and its influence on the electronic structure. The signal in the δ 1.0–1.5 ppm region is very clean, a clear characteristic of the tert-butyl group in the molecule. Two sharp tert-butyl singlets appeared at δ 1.37 ppm and δ 1.31 ppm, indicating the presence of two tert-butyl groups with different chemical environments in the molecule. These tert-butyl groups are located on the benzene rings connected by oxygen atoms at both ends of the molecule. Due to their different positions in the large rigid molecular skeleton, they have slight differences in chemical environment, which result in two independent signals on the NMR spectrum. The NMR spectrum is highly consistent with the theoretical prediction of [7]BO-PP, which strongly proves that the helical chiral peropyrene derivative [7]BO-PP has been synthesized.

[0088] Figure 2 The single-crystal structure spectrum of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 is shown. Figure 2Figure (a) shows the molecular structures of the enantiomers (P,P) and (M,M), where (P,P) represents right-handed helical units and (M,M) represents left-handed helical units. Figure 2 Figure (b) shows the molecular packing pattern in the unit cell. Yellow and white in the figure represent carbon and hydrogen atoms, which constitute the conjugated skeleton of peropyrene; red atoms correspond to oxygen atoms in boron-oxygen heterocycles, reflecting the structural features of boron-oxygen heterocycle modification; pink atoms correspond to boron atoms in boron-oxygen heterocycles; the molecular skeleton of the helical chiral peropyrene derivative [7] BO-PP is not a planar structure, but exhibits two obvious helical twists, a helical conjugated system formed by the fusion of 7 aromatic rings in adjacent positions, which is the source of helical chirality. The positions of boron and oxygen atoms can be identified at the key sites of the molecule. They are precisely embedded in the designed six-membered rings, forming a stable boron-oxygen heterocycle structure. This directly proves that the synthetic route successfully introduced heteroatoms into the carbon skeleton. The huge tert-butyl groups on the periphery of the molecule not only improve the solubility of the molecule, but also prevent excessive π-π interactions when the molecule is packed through the steric hindrance effect, thereby stabilizing the entire helical chiral configuration.

[0089] Figure 3The UV-Vis absorption spectra of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 in different solvents are shown. As can be seen from the figure, the absorption peaks of the helical chiral peropyrene derivative [7] BO-PP in different solvents are concentrated in the range of 300-500 nm, indicating that its large π-conjugated skeleton is not destroyed in different solvents and its structural stability is good. The absorption intensity of the helical chiral peropyrene derivative [7] BO-PP in nonpolar or weakly polar solvents such as hexane, toluene, o-dichlorobenzene (o-DCB), dichloromethane (DCM) and chloroform (CHCl3) is sharper than the peak shape. The interaction between the nonpolar or weakly polar solvent and the molecule is weak, and the conjugated skeleton of the molecule is closer to the "intrinsic state". The probability of π→π* transition is higher, so the absorption is stronger. The helical chiral peropyrene derivative [7] BO-PP exhibits relatively low absorption in strongly polar solvents such as tetrahydrofuran (THF), acetone, acetonitrile (MeCN), and N,N-dimethylformamide (DMF), with a slight "red shift" in the absorption peak. This may be because the strongly polar solvents form a polar interaction with the boron-oxygen heterocycle and chiral skeleton of [7] BO-PP, stabilizing the electronically excited state and reducing the transition energy, thus causing the absorption peak to red shift. The absorption peaks of the helical chiral peropyrene derivative [7] BO-PP in Lewis basic solvents such as triethylamine (Et3N) and pyridine show significant changes, indicating that the boron atoms in the molecular structure interact with the solvent, playing a regulatory role in the ground-state structure of the compound.

[0090] Figure 4 The images show the fluorescence emission spectra of the helical chiral peropyrene derivative [7]BO-PP prepared in Example 1 in different solvents. In Lewis basic solvents with weak coordination ability, its fluorescence emission wavelength changes significantly, indicating that the boron atoms in the [7]BO-PP molecular structure interact with the solvent, which plays a regulatory role in the excited state structure of the compound.

[0091] Figure 5 The UV-Vis absorption spectrum of the helical chiral peropyrene derivative [7]BO-PP prepared in Example 1, obtained by chemical titration of tetrabutylammonium fluoride in tetrahydrofuran solvent. With the addition of tetrabutylammonium fluoride, the absorption spectrum of [7]BO-PP changed significantly, indicating that there is an interaction between the boron atom and the fluoride ion in its molecular structure. Through data fitting, it was revealed that the number of sites coordinated with the fluoride ion in the molecular structure is 2.

[0092] Figure 6The visible light region fluorescence emission spectrum of the helical chiral peropyrene derivative [7]BO-PP prepared in Example 1, obtained by chemical titration of tetrabutylammonium fluoride in tetrahydrofuran solvent. With the addition of tetrabutylammonium fluoride, the fluorescence emission wavelength of [7]BO-PP first red-shifted and then blue-shifted, indicating that the emission wavelength of the material can be dynamically controlled by the addition of anions.

[0093] Figure 7 The cyclic voltammetry diagram of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 in dichloromethane solvent. The internal standard for the cyclic voltammetry was ferrocene. Figure 7 The potential is relative to ferrocene. [7] BO-PP exhibits two consecutive redox peaks, the first of which is reversible, indicating that stable cationic and anionic free radical species can be formed.

[0094] Figure 8 The circular dichroism absorption spectrum of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 in dichloromethane solvent. [7] BO-PP has a pair of enantiomers (M,M) and (P,P), which can exist stably at room temperature without racemization. Therefore, the chiral isomers can be obtained separately by chiral chromatography, exhibiting symmetrical circular dichroism spectra with opposite Cotton effects.

[0095] Figure 9 The image shows the circularly polarized emission spectrum of the helical chiral peropyrene derivative [7] BO-PP prepared in Example 1 in dichloromethane solvent. Similar to the circular dichroism absorption spectrum, the enantiomers (M,M) and (P,P) exhibit mirror symmetry in circularly polarized emission, showing circularly polarized emission activity.

[0096] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A helical chiral peropyrene derivative, characterized in that, It has a structure as shown in Equation I: 。 2. A method for preparing the helical chiral peropyrene derivative as described in claim 1, characterized in that, Includes the following steps: S1, 1,3-dibromo-2-iodobenzene and 1,4-phenylenediboronic acid were coupled via a palladium-catalyzed Suzuki reaction to give 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl; S2, dibromo-1,4-difluorobenzene and 4-tert-butylphenol undergo an aromatic nucleophilic substitution reaction in the presence of potassium carbonate to give 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene); S3. The 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) described in step S2 undergoes a lithiation reaction with n-butyllithium to generate a lithium reagent, which then undergoes a stepwise reaction with boron tribromide. Specifically, the boron atom is first introduced into a specific site on the aromatic ring through an aromatic electrophilic substitution reaction, and then a six-membered boron-oxygen heterocyclic structure is constructed through a direct carbon-hydrogen bond boration reaction to obtain 7-bromo-2,12-ditert-butyl-5,9-dioxa-13B-boronnaphthalene[3,2,1-DE]anthracene. S4. The 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-bornaphthalene[3,2,1-DE]anthracene described in step S3 is subjected to a palladium-catalyzed Miyaura borylation reaction to obtain 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene; S5. The 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl described in step S1 and the 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-”[3,2,1-DE]anthracene described in step S4 undergo a palladium-catalyzed Suzuki coupling reaction to obtain the precursor compound. S6. Under the action of the oxidant ferric chloride, the reaction precursor compound described in step S5 undergoes an intramolecular oxidative dehydrogenation cyclization reaction, simultaneously realizing the construction of the double [7] helical chiral framework and the stable insertion of boron-oxygen heteroatoms, to obtain peropyrene derivatives with extended double [7] helical chirality.

3. The method for preparing the helical chiral peropyrene derivative according to claim 2, characterized in that, The specific process of step S1 includes: adding the 1,3-dibromo-2-iodobenzene, the 1,4-phenylenediboric acid, a base reagent and a palladium catalyst to a mixed solvent containing an organic solvent and water; after purging the atmosphere with nitrogen, heating to a set temperature for reaction; and after the reaction is completed, extracting, concentrating and separating by column chromatography to obtain 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl.

4. The method for preparing the helical chiral peropyrene derivative according to claim 3, characterized in that, The mass ratio of the 1,3-dibromo-2-iodobenzene to the 1,4-phenylenediboronic acid is (4.3-5):1; And / or, the alkaline reagent is sodium bicarbonate, and the mass ratio of 1,4-phenylenediboric acid to sodium bicarbonate is 1:(2.89-3.0); And / or, the mixed solvent is composed of dimethyl sulfoxide and water, wherein the volume ratio of dimethyl sulfoxide to water is (5-7):1; And / or, the palladium catalyst is [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride dichloromethane complex, and the mass ratio of the catalyst to the 1,4-phenylenediboric acid is 1:(3.0-3.2); And / or, the nitrogen replacement is carried out by nitrogen bubbling, the nitrogen bubbling time is 15-25 min; the set temperature is 60-70 ℃, the reaction time is 2-4 days; the extraction reagent is ethyl acetate, and the extraction is performed 2-4 times.

5. The method for preparing the helical chiral peropyrene derivative according to claim 2, characterized in that, The specific process of step S2 includes: under a nitrogen atmosphere, mixing the 2,5-dibromo-1,4-difluorobenzene, the 4-tert-butylphenol, the alkaline reagent and the organic solvent, heating to a set temperature for reaction, and after the reaction is completed, extracting, concentrating and separating by column chromatography to obtain 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene).

6. The method for preparing the helical chiral peropyrene derivative according to claim 5, characterized in that, The mass ratio of 2,5-dibromo-1,4-difluorobenzene to 4-tert-butylphenol is 1:(1.6-1.7). And / or, the alkaline reagent is potassium carbonate, and the mass ratio of 2,5-dibromo-1,4-difluorobenzene to potassium carbonate is 1:(1.5-1.6); And / or, the organic solvent is anhydrous N-methylpyrrolidone, and the ratio of 2,5-dibromo-1,4-difluorobenzene to anhydrous N-methylpyrrolidone is 1 g:(4-5) mL; And / or, the set temperature is 160-180 ℃, and the reaction time is 18-22 h; And / or, the extraction reagent is dichloromethane, and the extraction is performed 2-4 times.

7. The method for preparing the helical chiral peropyrene derivative according to claim 2, characterized in that, The specific process of step S3 includes: under a nitrogen atmosphere, dissolving the 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) in an organic solvent, and after a lithiation reaction, adding the boron tribromide to carry out a swelling reaction, and then adding an organic amine reagent to carry out a multi-stage temperature gradient reaction. After the reaction is completed, quenching, filtration, concentration, and column chromatography separation are performed to obtain 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronnaphthalene[3,2,1-DE]anthracene.

8. The method for preparing the helical chiral peropyrene derivative according to claim 7, characterized in that, The organic solvent is anhydrous meta-xylene, and the ratio of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) to anhydrous meta-xylene is 1 g:(9-11) mL; And / or, the lithiation reaction is carried out at a temperature of -85 to -75 °C for a time of 1.5 to 2.5 h; And / or, the lithiumizing agent is n-butyllithium with a concentration of 1.2-2 mol / L, and the ratio of the amount of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) to the amount of n-butyllithium is 1 g:(1.1-1.2) mL; And / or, the concentration of boron tribromide is 1.6-2.5 mol / L, and the ratio of the amount of 4,4'-((2,5-dibromo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) to the amount of boron tribromide is 1 g:(1.0-1.2) mL; And / or, the initial temperature of the borylation reaction is -85 to -75 °C, the reaction time is 0.8 to 1.2 h, then the temperature is restored to room temperature for 25 to 35 min, and then the temperature is raised to 40 to 50 °C for 0.8 to 1.2 h. And / or, the multi-stage temperature gradient reaction includes: after the borylation reaction, the temperature is first lowered to 0-5 ℃, the organic amine reagent is added, the reaction time after returning to room temperature is 25-35 min, and finally the temperature is raised to 130-140 ℃ and the reaction is carried out for 18-22 h; And / or, the quenching agent is methanol.

9. The method for preparing the helical chiral peropyrene derivative according to claim 2, characterized in that, The specific process of step S4 includes: adding the 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-borona[3,2,1-DE]anthracene, pinacol diboronate, alkaline reagent and palladium catalyst to an organic solvent; after purging the atmosphere with nitrogen, heating to a set temperature for reaction; after the reaction is completed, extraction, concentration and column chromatography are performed to obtain 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxa-13B-borona[3,2,1-DE]anthracene.

10. The method for preparing the helical chiral peropyrene derivative according to claim 9, characterized in that, The mass ratio of the 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-borona[3,2,1-DE]anthracene to the pinacol diboronic acid ester is 1:(0.8-0.9); And / or, the alkaline reagent is potassium acetate, and the mass ratio of the 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronnaphthalene[3,2,1-DE]anthracene to the potassium acetate is 1:(2.0-2.2); And / or, the organic solvent is 1,4-dioxane, and the ratio of the amount of 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronnaphthalene[3,2,1-DE]anthracene to the amount of 1,4-dioxane is 1 g:(45-55) mL; And / or, the palladium catalyst is 1,1'-bis(diphenylphosphine)ferrocene palladium dichloride, and the mass ratio of the palladium catalyst to the 7-bromo-2,12-di-tert-butyl-5,9-dioxa-13B-boronnaphthalene[3,2,1-DE]anthracene is 1:(20-22); And / or, the nitrogen replacement is carried out by nitrogen bubbling, and the nitrogen bubbling time is 15-25 min; And / or, the extraction reagent is dichloromethane, and the extraction is performed 2-4 times.

11. The method for preparing the helical chiral peropyrene derivative according to claim 2, characterized in that, The specific process of step S5 includes: adding the 2,2”,6,6”-tetrabromo-1,1':4',1”-terphenyl and the 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-bornaphthalene[3,2,1-DE]anthracene, a base reagent and a palladium catalyst to a mixed solvent composed of an organic solvent and water. After purging the atmosphere with nitrogen, the mixture is heated to a set temperature to carry out a Suzuki coupling reaction. After the reaction is completed, the precursor compound is obtained by extraction, concentration and column chromatography.

12. The method for preparing the helical chiral peropyrene derivative according to claim 11, characterized in that, The mass ratio of the 2,2”,6,6”-tetrabromo-1,1':4',1”-terphenyl to the 2,12-di-tert-butyl-7-(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl)-5,9-dioxo-13B-boronaphthyl[3,2,1-DE]anthracene is 1:(7.0-7.5). And / or, the alkaline reagent is potassium carbonate, and the mass ratio of 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl to potassium carbonate is 1:(3.8-4.0); And / or, the mixed solvent is composed of 1,4-dioxane and water, wherein the volume ratio of 1,4-dioxane to water is (5-7):1; And / or, the ratio of the amount of 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl to the amount of the mixed solvent is 1 g:(120-130) mL; And / or, the palladium catalyst is tetratriphenylphosphine palladium, and the mass ratio of the palladium catalyst to 2,2”,6,6”-tetrabromo-1,1’:4’,1”-terphenyl is 1:(3.7-3.9); And / or, the nitrogen replacement is carried out by nitrogen bubbling, and the nitrogen bubbling time is 15-25 min; And / or, the set temperature is 95-105 °C; the Suzuki coupling reaction time is 22-26 h; And / or, the extraction reagent is dichloromethane, and the extraction is performed 2-4 times.

13. The method for preparing the helical chiral peropyrene derivative according to claim 2, characterized in that, The specific process of step S6 includes: dissolving the reaction precursor compound in a dry organic solvent, replacing the atmosphere with nitrogen, adding a ferric chloride nitromethane solution dropwise under refrigeration and temperature control, sealing and stirring to carry out an intramolecular oxidative dehydrogenation cyclization reaction, and after the reaction is completed, obtaining the peropyrene derivative with boron-oxygen double helical chirality extension by quenching, filtration and column chromatography.[7] 14. The method for preparing the helical chiral peropyrene derivative according to claim 13, characterized in that, The organic solvent is dichloromethane, and the ratio of the reaction precursor compound to dichloromethane is 1g:(550-600)mL; And / or, the mass ratio of the reaction precursor compound to the ferric chloride is 1:(5.5-5.6); And / or, the ratio of ferric chloride to nitromethane is 1 g:(11-12) mL; And / or, the temperature of the cooling temperature control is -5 to 5°C; And / or, the intramolecular oxidative dehydrogenation cyclization reaction takes 25-35 min; And / or, the quenching agent is methanol.

15. An organic electronic device, characterized in that, It includes an active layer comprising the helical chiral peropyrene derivative of claim 1.

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